JPH06202259A - Silver halide photographic sensitive material containing polymer latex - Google Patents

Abstract

PURPOSE:To prevent fluctuation of photographic performances due to long storage of the polymer latex and stagnation of a coating fluid by incorporating a compound for preventing propagation of microorganisms. CONSTITUTION:The photographic sensitive material contains the polymer latex stabilized with a gelatin in at least one of emulsion layers and/or hydrophilic colloidal layers, and the polymer latex contains the compound preventing propagation of microorganisms, exemplified by the formula in which R<1> is H, an alkyl, alkenyl, aralkyl, aryl, or a heterocyclic group; each of R<2> and R<3> is H, a halogen, alkyl, aryl, cyano, alkylthio, heterocyclic group, aralkylthio, alkylsulfoxy, or an alkylsulfonyl, thus permitting the propagation of microorganisms to be prevented in the long storage and during the stagnation of the coating fluid and occurrence of coating trouble, such as trailing and uneven coating to be prevented.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a polymer latex. The light-sensitive material of the present invention can be used as various light-sensitive materials including printing plate-making light-sensitive materials.

[0002]

BACKGROUND OF THE INVENTION In silver halide photographic light-sensitive materials, gelatin is generally widely used as a binder.
However, since the structure of the gelatin film is not the same before and after the development processing, development occurs in which the dimensions of the photosensitive material are different before and after the processing. On the other hand, it is well known that the inclusion of the polymer latex in the light-sensitive material improves the dimensional maintenance before and after processing. However, when a large amount of polymer latex is added, the physical properties of the light-sensitive material are deteriorated, which is not preferable. Therefore, Japanese Patent Application Nos.
92175 proposed a technique using a polymer latex stabilized with gelatin.

However, in the polymer latex stabilized with gelatin, if microorganisms are mixed in during handling, the microorganisms will propagate during long-term storage or during stagnation of the coating solution, which will cause a change in photographic performance and / or microorganisms. The colonies serve as nuclei to cause coating failure (tailing) during coating, and uneven coating due to a decrease in viscosity is not preferable.

[0004]

An object of the present invention is to provide a silver halide photographic light-sensitive material containing a polymer latex for the purpose of improving dimensional properties, which solves the above problems and prevents the microorganisms from being stored during long-term storage of the latex and stagnant coating solution. The purpose of the present invention is to provide a silver halide photographic light-sensitive material that prevents breeding, does not cause coating failures such as tailing and coating unevenness, and does not fluctuate in photographic performance during long-term storage of latex, stagnation of coating solution, etc. To do.

[0005]

The invention according to claim 1 of the present application relates to a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support. Layer and / or at least one of the hydrophilic colloid layers contains a gelatin-stabilized polymer latex, and contains a compound for preventing the growth of microorganisms. A photographic light-sensitive material which achieves the above object.

In the invention of claim 2 of the present application, the compound for preventing the growth of microorganisms is arbitrarily selected from the group of compounds consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II). The silver halide photographic light-sensitive material containing a polymer latex according to claim 1, wherein the silver halide photographic light-sensitive material is a compound selected from at least one compound.

[0007]

[Chemical 4]

In the general formula (I), R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group,

[0009]

[Chemical 5]

R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkylsulfoxy group or an alkylsulfonyl group. R ² and R ³ may combine with each other to form an aromatic. R ⁴ and R ⁵ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

[0011]

[Chemical 6]

In the general formula (II), R ⁷ represents a hydrogen atom, an alkyl group or a hydroxymethyl group. R ⁸ represents a hydrogen atom or an alkyl group.

The invention according to claim 3 of the present application is characterized in that the compound for preventing the growth of microorganisms is contained in advance in the gelatin-stabilized polymer latex. A silver halide photographic light-sensitive material containing latex, which achieves the above object.

The invention according to claim 4 of the present application is characterized in that a compound for preventing the growth of microorganisms is added at the time of preparing a coating solution, and the silver halide photographic light-sensitive material containing a polymer latex according to claim 1 or 2. A material, which achieves the above object.

In the present invention, the compound for preventing the growth of microorganisms is preferably contained in the light-sensitive material in an amount of 0.001 to 10 mg / m ² . When it is added to the polymer latex liquid or the coating liquid, it is preferably contained at a concentration of 1 to 1000 ppm.

Next, the compound of the general formula (I) or (II) which can be used as a compound for preventing the growth of microorganisms will be explained.

In the general formula (I), when R ¹ is an alkyl group, it may be linear, branched or cyclic. When R ² and R ³ are alkyl groups, they may be cyclic.

More specifically, in the general formula (I), R
¹ is a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, tert-
Butyl group, n-octadecyl group, 2-hydroxyethyl group, 2-carboxyethyl group, 2-cyanoethyl group, sulfobutyl group, N, N-dimethylaminoethyl group, etc.), substituted or unsubstituted cyclic alkyl group (eg cyclohexyl) Group, 3-methylcyclohexyl group, 2-oxocyclopentyl group, etc.), substituted or unsubstituted alkenyl group (eg, allyl group, methylallyl group, etc.), substituted or unsubstituted aralkyl group (eg, benzyl group, p-
Methoxybenzyl group, o-chlorobenzyl group, p-is
o-propylbenzyl group), a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group, o-methylphenyl group, m-nitrophenyl group, 3,4-dichlorophenyl group, etc.), heterocyclic group, (2 An imidazolyl group,
2-furyl group, 2-thiazolyl group, 2-pyridyl group, etc.),

[0019]

[Chemical 7]

R ² and R ³ are each a hydrogen atom, a halogen atom (eg, chloro group, butyl group, etc.) and a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, chloromethyl group, 2-hydroxyethyl group, tert. -Butyl group, n
-Octyl group), substituted or unsubstituted cyclic alkyl group (eg cyclohexyl group, 2-oxocyclopentyl group etc.), substituted or unsubstituted aryl group (eg phenyl group, 2-methylphenyl group, 3,4-dichlorophenyl) Group, naphthyl group, 4-nitrophenyl group, 4-aminophenyl group, 3-acetamidophenyl group, etc.),
Cyano group, heterocyclic group (for example, 2-imidazolyl group, 2
-Thiazolyl group, 2-pyridyl group, etc.), substituted or unsubstituted alkylthio group (e.g., methylthio group, 2-cyanoethylthio group, 2-ethoxycarbonylthio group, etc.), substituted or unsubstituted arylthio group (e.g., phenylthio group, 2-carboxyphenylthio group, p-methoxyphenylthio group, etc.), substituted or unsubstituted alkylsulfoxy group (eg, methylsulfoxy group, 2-hydroxyethylsulfoxy group, etc.), substituted or unsubstituted alkylsulfonyl group (For example, a methylsulfonyl group, 2
-Bromoethylsulfonyl group) and R ² and R ³ may be bonded to each other to form an aromatic group (eg, benzene ring, naphthalene ring, etc.).

R ⁴ and R ⁵ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, iso)
-Propyl group, 2-cyanoethyl group, 2-n-butoxycarbonylethyl group, 2-cyanoethyl group, etc.) or a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group, 2-methoxyphenyl group, m-nitrophenyl) Group, 3,5-dichlorophenyl group, 3-acetamidophenyl group, etc.), a substituted or unsubstituted aralkyl group (for example, benzyl group, phenethyl group, p-iso-propylbenzyl group, o-chlorobenzyl group, m-methoxybenzyl group) Group).

Next, typical examples of the compound represented by the general formula (I) (hereinafter referred to as compound I) are shown below. However, the compound I that can be used in the present invention is not limited to these.

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

Some of the above compounds are commercially available and can be easily obtained.
It can be synthesized according to the synthesis method described in No. 555,416.

Next, the compound represented by the general formula (II) will be described in detail. In the formula, R ⁷ represents a hydrogen atom, a lower alkyl group (for example, a methyl group, an ethyl group, an iso-propyl group, etc.) or a hydroxymethyl group, and R ⁸ represents a hydrogen atom, a lower alkyl group (for example, a methyl group, n- Butyl group, is
o-amyl group). The lower alkyl group preferably has 1 to 5 carbon atoms, particularly 1 carbon atom.

Typical examples of the compound represented by the general formula (II) (hereinafter referred to as compound II) are shown below. However, the compound II that can be used in the present invention is not limited to these.

[0033]

[Chemical 15]

Some of these compounds are commercially available from Mitsubishi Oil Corporation. Moreover, it can be synthesized with reference to the following documents. Henry Recueil des trava
ux chiniques des Rays-Bas
16 251 Mass. chemisches Zentralb
latt 1899 I179 E.I. Schmidt. Berichte der D
euchen Chemischen Gesell
schaft. 52 397 E.I. Schmidt. ibid 55 317 Henry Chemiches Zentralb
latt. 1897 II 338

In this case, the synthesis of Compound Example II-1 was carried out in the literature,
, II-2 can be synthesized according to the literature, II-3 can be synthesized according to the literature, and II-4 can be synthesized according to the literature.

The compound I and the compound II can be used by adding, for example, to a hydrophilic colloid for forming a light-sensitive material.
The use in such a case is described in JP-A-54-27420,
It is known by the above-mentioned 59-226343 and 60-119547.

As a result of detailed investigations, the present inventors have found that compound I or compound II has an effect of preventing the growth of microorganisms by a latex stabilized with gelatin, and completed the present invention.

The compounds I and II of the present invention may be dissolved in water or an organic solvent such as methanol, isopropanol, acetone or ethylene glycol, which does not adversely affect the photographic performance, and added as a solution.

In the present invention, the gelatin-stabilized polymer latex is obtained by carrying out at least a part of the polymerization reaction of the polymer in a solvent containing at least gelatin.

The amount of the polymer latex added to the light-sensitive material is preferably 0.05 to 5 g / m ^{2 on} one side, and is 0.1.
-2.5 g / m < ² > is more preferable.

The polymer latex used in the present invention can change the MFT (minimum film forming temperature) depending on the composition of the monomer, but it is particularly effective when the MFT is 60 ° C. or lower, more preferably the MFT is 50. It is below ℃.

Furthermore, in the present invention, the particle size of the latex is 0.3 μm.
It is preferably m or less. A particularly preferred particle size is 0.
It is from 01 to 0.27 μm, and particularly from 0.01 to 0.20 μm.

The constitution of the monomer of the polymer latex contained in the photographic light-sensitive material of the present invention is, for example, US Pat. Nos. 2,772,166, 3,325,286, 3,411,911 and 3,211. 311,912, 3,525,620, Research Disclosure N
o. 195 19551 (July 1980) and the like, acrylates, methacrylic acid esters, hydrates of vinyl polymers such as styrene, and the like can be used as the monomer component.

Examples of gelatin used for stabilizing the latex include gelatin and gelatin derivatives, cellulose derivatives, and graft polymers of gelatin and other polymers. Other proteins, sugar derivatives, cellulose derivatives, single or A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used in combination.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, buretin of society
Of Japan (Bull. Soc. Sci. Pho
t. The acid-processed gelatin as described in Japan No. 16, page 30 (1966) may be used, and a hydrolyzate or enzymatic hydrolyzate of gelatin may also be used.
Examples of the gelatin derivative include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, and epoxy compounds in gelatin. What is obtained by reacting with can be used. Specific examples thereof are US Pat. No. 2,614,92.
No. 8, No. 3,132,945, No. 3,186,846
No. 3,312,553, British Patent 861,414
Issue 1,033,189, Issue 1,005,784
And Japanese Examined Patent Publication No. 2626845.

Examples of proteins include albumin, casein,
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, a sulfuric acid ester of cellulose, or as the sugar derivative, sodium alginate or a starch derivative may be used in combination with gelatin.

As the graft polymer of gelatin and other polymers, gelatin is a homopolymer of acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and vinyl monomers such as acrylonitrile and styrene. The thing which grafted the copolymer can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a copolymer such as acrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. Examples of these are US Pat. Nos. 2,763,625 and 2,831,
767, 2,956,884 and the like.

In the present invention, the polymer latex is
It is contained in at least one light-sensitive silver halide emulsion layer and / or at least one non-light-sensitive hydrophilic colloid layer. It may be added in any other layer. It may be contained on only one side of the support, or may be contained on both sides. When included on both sides of the support, the type and / or amount of polymer latex included on each side may be the same or different.

Examples of the monomer component of the latex contained in the photographic light-sensitive material of the present invention include those represented by the general formula [I] and, for example, US Pat. No. 2,772,166.
Issue 3, Issue 3,325,286, Issue 3,411,911
No. 3,311,912, No. 3,525,620
Issue, Research Disclosure
Disclosure) No. 19519551 (1
Acrylic acid ester, methacrylic acid ester, hydrates of vinyl polymers such as styrene as described in (July 980) and the like may be contained. Specifically, acrylic acid, methacrylic acid or salt, maleic acid or salt,
Fumaric acid or salt, alkyl acrylate such as methyl acrylate and ethyl acrylate, metaalkyl acrylate such as methyl methacrylate and ethyl methacrylate, styrene, styrenesulfonic acid or salt, N-substituted or unsubstituted acrylamide, vinyl alcohol , Hydroxyalkyl methacrylates,
Any compound having a double bond such as butadiene can be selected as a copolymerization component as a monomer.

Specific examples of preferable monomers are shown below. The latex used in the photographic light-sensitive material of the present invention can take any combination (type, composition ratio) of these monomers. Needless to say, what can be used in the present invention is not limited to these monomers.

[0051]

[Chemical 16]

[0052]

[Chemical 17]

[0053]

[Chemical 18]

[0054]

[Chemical 19]

[0055]

[Chemical 20]

In the silver halide photographic light-sensitive material of the present invention, the total amount of hydrophilic binders on the side having the light-sensitive silver halide emulsion layer with respect to the support is 3.5 g / m ² or less. preferable.

There are no particular restrictions on other general additives and known contrast-increasing agents, as well as the method for producing silver halide grains and the method for sensitizing, which constitute the light-sensitive material of the present invention. Kaihei 1-230035, Japanese Patent Application 1-2
These can be selected by referring to the description of No. 66640 and the like.

In the present invention, one or more antistatic layers may be provided on the support, for example, on the backing side and / or the emulsion layer side, for the purpose of antistatic property which is another physical property of the light-sensitive material. .

In this case, the surface resistance on the side provided with the antistatic layer is preferably 1.0 × 10 ¹² Ω or less at 25 ° C. and 50%, and particularly preferably 8 × 10 ¹¹ Ω or less.

The antistatic layer is preferably an antistatic layer containing a water-soluble conductive polymer, hydrophobic polymer particles and a reaction product of a curing agent, or an antistatic layer containing a metal oxide.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group polyethylene oxide group. Can be mentioned. Of these groups, a sulfonic acid group, a sulfuric acid ester group and a quaternary ammonium salt group are preferred. The amount of the conductive group is preferably 5% by weight or more per molecule of the water-soluble conductive polymer.

When a water-soluble conductive polymer containing a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinyl sulfone group or the like is used. Of these, those containing a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, and an aldehyde group are preferable. It is preferable that these groups are contained in an amount of 5% by weight or more per polymer molecule. The number average molecular weight of the water-soluble conductive polymer is preferably 300.
0 to 100,000, and more preferably 3500 to
It is 50,000.

As the above-mentioned metal oxide, tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide, or a substance obtained by doping these metal oxides with metal phosphorus, metal silver, or metal indium is preferable. Used. The average particle size of these metal oxides is 1μ
˜0.01 μ is preferable.

As the undercoat layer which can be used in the present invention, an undercoat layer in an organic solvent system containing polyhydroxybenzenes described in JP-A-49-3972, JP-A-4.
9-11118, 52-104913, 59-
No. 19941, No. 59-19940, No. 59-189.
No. 45, No. 51-112326, No. 51-11761
No. 7, No. 51-58469, No. 51-114120
No. 51-121323, No. 51-123139.
No. 51-114121, No. 52-139320
No. 52-65422, No. 52-109923,
No. 52-119919, No. 55-65949, No. 5
Examples of the aqueous latex undercoating layer described in JP-A Nos. 7-128332 and 59-19941 include U.S. Pat. Nos. 2,698,235 and 2,779,684.
Examples thereof include vinylidene chloride-based undercoating described in Nos. 425,421 and 4,645,731.

The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and surface activation treatment such as ozone oxidation treatment. .

There is no limitation on the coating timing and conditions of the undercoat layer and other coating layers.

In the present invention, a usual water-soluble dye may be used, and a solid-dispersed dye may be contained in any hydrophilic colloid layer. The layer may be the outermost layer on the emulsion surface side, or may be added below the emulsion layer and / or on the backing surface side for the purpose of preventing halation. Also, an appropriate amount may be added to the emulsion layer for adjusting the irradiation. Of course, plural kinds of solid disperse dyes may be contained in plural layers.

[0068] The amount of solid disperse dye is preferably 5mg / m ² ~1g / m ² per kind, particularly preferably ^{10mg / m 2 ~800mg / m 2} .

The fine particles of the solid dispersion to be used are obtained by pulverizing the dye with a dispersing machine such as a ball mill or a sand mill, and then water or a hydrophilic colloid such as gelatin, sodium dodecylbenzenesulfonate, sodium fluorinated octylbenzenesulfonate. , Saponin, nonylphenoxy polyethylene glycol and the like can be dispersed and obtained.

Examples of the general formula of the solid disperse dye include those described in US Pat. No. 4,857,446 and the like. For example, those represented by the general formulas [I] to [V] of the same specification. Is preferably used.

The present invention can be applied to various photosensitive materials for printing, X-ray, general negative, general reversal, general positive and direct positive. In particular, when it is applied to a photosensitive material for printing which requires extremely high dimensional stability, a remarkable effect can be obtained.

In processing the silver halide photographic light-sensitive material of the present invention, the development temperature is preferably 50 ° C. or less, and particularly 2
The temperature is preferably about 5 ° C. to 40 ° C., and the development processing time is generally completed within 2 minutes, but it is particularly preferable to perform rapid processing for 5 to 60 seconds.

[0073]

EXAMPLES Examples of the present invention will be specifically described below. However, it goes without saying that the present invention is not limited to this embodiment.

Example 1 (Latex Synthesis Method) Gelatin was added to 40 liters of water in an amount of 0.
To a liquid added with 4 kg and 0.05 kg of ammonium persulfate, while stirring at a liquid temperature of 80 ° C., a mixed liquid of monomer components as shown below was added over 1 hour under a nitrogen atmosphere, and then for 1.5 hours. After stirring, 0.3 kg of gelatin was added, and the mixture was stirred for 1.5 hours. After completion of the reaction, steam distillation was carried out for another 1 hour to remove residual monomers, and after cooling to room temperature, the pH was adjusted to 6.0 with ammonia. It was adjusted. The obtained latex liquid (latex Lx-1) was 50.
Finished to 5 kg. The solid content was 15 wt%. Latex Lx-1 Monomer giving L-1 2.0 kg Monomer giving L-7 3.0 kg Monomer giving L-9 1.5 kg Monomer giving L20 0.4 kg

(Emulsion preparation) A silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × rhodium hexachloride complex.
The solution added so as to have a concentration of 10 ⁻⁵ mol / Ag mol was simultaneously added to the gelatin solution while controlling the flow rate, and after desalting, a cubic crystal containing 0.13 μ in particle size and 1 mol% of silver bromide was added. dispersion,
A silver chlorobromide emulsion was obtained.

This emulsion was sulfur-sensitized in the usual way to give 6-methyl-4-hydroxy-1,3,3 as a stabilizer.
After adding a, 7 tetrazaindene, the following additives were added to prepare an emulsion coating solution, and then emulsion protective layer coating solution P-
0, backing layer coating liquid B-0 and backing protective layer coating liquid BP-0 were prepared with the following compositions.

(Preparation of Emulsion Coating Solution) Compound (a) shown in Table 1 Amount shown in Table 1 NaOH (0.5N) pH adjusted to 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² Saponin (20%) 0.5 cc / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg / m ² compound (f) 6 mg / M ² latex Lx-1 1 g / m ² styrene-maleic acid copolymer polymer (thickener) 90 mg / m ²

[0078]

[Chemical 21]

(Emulsion protective layer coating liquid P-0) Gelatin 0.5 g / m ² compound (g) (1 wt% aqueous solution) 25 cc / m ² compound (h) 120 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² Spherical monodisperse silica (3 μm) 10 mg / m ² compound (i) 100 mg / m ² citric acid pH adjusted to 6.0

(Backing Layer Coating Solution B-0) Gelatin 1.0 g / m ² compound (j) 100 mg / m ² compound (k) 18 mg / m ² compound (l) 100 mg / m ² saponin (20 wt% aqueous solution) 0 0.6 cc / m ² latex (m) 300 mg / m ² 5-nitroindazole 20 mg / m ² styrene-maleic acid copolymer polymer (thickener) 45 mg / m ² glyoxal 4 mg / m ² compound (o) 100 mg / m ²

(Backing Protective Layer Coating Liquid BP-0) Gelatin 0.5 g / m ² Compound (g) (1 wt% aqueous solution) ² cc / m ² Spherical polymethylmethacrylate (4 μ) 25 mg / m ² Sodium chloride 70 mg / m ² Glyoxal 22 mg / m ² Compound (n) 10 mg / m ²

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

On the side of the emulsion surface of the polyethylene terephthalate base having a thickness of 100 μm, which has been subjected to the undercoating shown in JP-A-59-19941, there is 10 W /
After the corona discharge was applied at (m ² · min), the following composition was applied using a roll-fit coating van and an air knife. Drying was performed at 90 ° C under a parallel flow drying condition with a general heat transfer coefficient of 25 Kcal (m ² · hr · ° C).
It was carried out for 0 minutes, and subsequently at 140 ° C. for 90 seconds. The thickness of this layer after drying was 1 μm, and the surface resistivity of this layer was 23 ° C. 5
It was 1 × 10 ⁸ Ω at 5%.

[0086]

[Chemical 25]

Ammonium sulfate 0.5 g / liter Polyethylene oxide compound (average molecular weight 600) 6 g / liter Curing agent 12 g / liter

[0088]

[Chemical formula 26]

On this base, formalin solution was used as a hardening agent solution in the order of emulsion layer and emulsion protective layer in order from the side closer to the support as the emulsion surface side, while keeping at 35 ° C. After applying the multi-layer coating at the same time, and passing through the cold air set zone (5 ° C), the backing layer and the backing protective layer are also applied while adding the hardener with the slide hopper, and the cold air set (5 ° C). )did. The coating liquid showed sufficient setting properties when passing through each set zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the backing surface side, the film was conveyed until it was wound up in a roller, without any contact with other parts. At this time, the coating speed was 100 m / min. Emulsion solutions having a dwell time of 1 hour and 12 hours were applied.

(Drying conditions) After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of H ₂ O / gelatin reached 800%,
Dry 800 to 200% with 35 ° C (30%) dry air, apply the air as it is, and after 30 seconds from the time when the surface temperature reaches 34 ° C (assuming drying is completed), 48 ° C 2% air for 1 minute Dried. At this time, the drying time is H
₂ O / gelatin ratio up to 800% for 50 seconds, 800% to 2
It takes 35 seconds from 00% to 5 seconds from 200% to the end of drying.

This light-sensitive material was wound at 23 ° C. 40%, then cut in the same environment, and conditioned in a barrier bag for 3 hours in the same environment, and then conditioned at 40 ° C. 10% for 8 hours.
It was sealed with cardboard which had been conditioned to 2% for 2 hours.

In the light-sensitive material produced as described above, the coated silver amount was 3.5 g / m ² and the gelatin amount was 1.5 g / m ² in the emulsion layer.

The prepared sample was used in a bright room printer P-62.
7FM (manufactured by Dainippon Screen Co., Ltd.) was processed through the wedge under the following standard processing conditions, and the sensitivity was evaluated. Further, exposure was performed so that the optical density was D = 1.0, and tailing and coating unevenness were evaluated. (Evaluation of tailing) Number of tailing per 10 cm ² (Evaluation of coating unevenness) 5: No coating unevenness 4: Some coating unevenness 3: Coating unevenness, practical level 2: Uneven coating unevenness, unusable 1: Very uneven coating

(Standard processing conditions) Development 28 ° C. 30 seconds Fixing 28 ° C. 20 seconds Water washing Normal temperature 15 seconds Drying 40 ° C. 35 seconds

<Developer formulation> (Composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methyl Benzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to bring the pH of the working solution to 10.9 Potassium bromide 4.5 g

(Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 mg Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg Developer At the time of use, the composition A and the composition B were dissolved in this order in 500 ml of water to make 1 liter.

<Fixer Formulation> (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate / trihydrate 15.9 g Boric acid 6.7 g Sodium citrate / dihydrate Salt 2g Acetic acid (90% W / V aqueous solution) 8.1 ml

(Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 5.8 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 26. When 5 g of the fixing solution was used, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 liter. The pH of this fixer was about 4.3.

The evaluation results are shown in Table 2.

[0100]

[Table 1]

[0101]

[Table 2]

As can be seen from Table 2, the samples according to the present invention have appropriate sensitivity and good storability, and as a result, the occurrence of coating failures such as tailing and coating unevenness is suppressed. Has been. According to this embodiment, it is possible to obtain a light-sensitive material in which variations in photographic performance are suppressed.

Example 2 To the latex liquid prepared in Example 1, the compounds of the present invention in the types and amounts shown in Table 3 were added and stored at 25 ° C. for 10 days, and then a sample was prepared in the same manner as in Example 1. Created and evaluated. The results are shown in Table 4.

[0104]

[Table 3]

[0105]

[Table 4]

As can be seen from Table 4, the same effects as in Example 1 could be obtained also in this Example.

[0107]

EFFECTS OF THE INVENTION According to the present invention, even when a polymer latex is added to improve the dimensional property, it is possible to prevent the growth of microorganisms during long-term storage of the latex, stagnant coating solution, etc. It is possible to provide a silver halide photographic light-sensitive material which does not cause coating failure such as unevenness and has no fluctuation in photographic performance during long-term storage of latex, stagnation of coating solution and the like.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support, wherein the emulsion layer and / or the hydrophilic colloid layer is A silver halide photographic light-sensitive material containing a polymer latex, wherein at least one of the layers contains a gelatin-stabilized polymer latex and a compound which prevents the growth of microorganisms. 2. A compound for preventing the growth of microorganisms, which is at least one selected from the group consisting of a compound represented by the general formula (I) and a compound represented by the general formula (II).
2. The silver halide photographic light-sensitive material containing a polymer latex according to claim 1, which is a compound of a kind. [Chemical 1] In formula (I), R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkylsulfoxy group, or an alkylsulfonyl group. R ² and R ³ may combine with each other to form an aromatic. R ⁴ and R ⁵ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. [Chemical 3] In formula (II), R ⁷ represents a hydrogen atom, an alkyl group, or a hydroxymethyl group. R ⁸ represents a hydrogen atom or an alkyl group. 3. A silver halide photographic light-sensitive material containing a polymer latex according to claim 1, wherein the compound for preventing the growth of microorganisms is contained in advance in the polymer latex stabilized with gelatin. . 4. The compound according to claim 1 or 2, wherein a compound that prevents the growth of microorganisms is added during the preparation of the coating solution.
The silver halide photographic light-sensitive material containing the polymer latex according to 1.